CN1292013A - Process for rigid polyurethane foams - Google Patents
Process for rigid polyurethane foams Download PDFInfo
- Publication number
- CN1292013A CN1292013A CN99803273A CN99803273A CN1292013A CN 1292013 A CN1292013 A CN 1292013A CN 99803273 A CN99803273 A CN 99803273A CN 99803273 A CN99803273 A CN 99803273A CN 1292013 A CN1292013 A CN 1292013A
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- China
- Prior art keywords
- pentane
- trimethylmethane
- iso
- mixture
- pentamethylene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 238000000034 method Methods 0.000 title claims description 20
- 229920005830 Polyurethane Foam Polymers 0.000 title description 3
- 239000011496 polyurethane foam Substances 0.000 title description 3
- 239000000203 mixture Substances 0.000 claims abstract description 53
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 claims abstract description 46
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000006260 foam Substances 0.000 claims abstract description 25
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims abstract description 23
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000004604 Blowing Agent Substances 0.000 claims abstract description 17
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims abstract description 16
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000011495 polyisocyanurate Substances 0.000 claims abstract description 11
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 21
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 12
- -1 functional group isocyanates Chemical class 0.000 claims description 11
- 239000012948 isocyanate Substances 0.000 claims description 8
- 150000002513 isocyanates Chemical class 0.000 claims description 5
- 229920001228 polyisocyanate Polymers 0.000 abstract description 10
- 239000005056 polyisocyanate Substances 0.000 abstract description 10
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 229920000582 polyisocyanurate Polymers 0.000 abstract description 2
- 239000004814 polyurethane Substances 0.000 abstract description 2
- 229920002635 polyurethane Polymers 0.000 abstract description 2
- 239000001282 iso-butane Substances 0.000 abstract 2
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 abstract 1
- 239000004033 plastic Substances 0.000 description 24
- 229920003023 plastic Polymers 0.000 description 24
- 238000005187 foaming Methods 0.000 description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 229930195733 hydrocarbon Natural products 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 150000002430 hydrocarbons Chemical class 0.000 description 5
- 150000005846 sugar alcohols Polymers 0.000 description 5
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 241000024287 Areas Species 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- XPDWGBQVDMORPB-UHFFFAOYSA-N Fluoroform Chemical compound FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 229920000265 Polyparaphenylene Polymers 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- 206010000269 abscess Diseases 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229960003132 halothane Drugs 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- VOZKAJLKRJDJLL-UHFFFAOYSA-N tolylenediamine group Chemical group CC1=C(C=C(C=C1)N)N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- 229960004418 trolamine Drugs 0.000 description 2
- 238000005491 wire drawing Methods 0.000 description 2
- MEIRRNXMZYDVDW-MQQKCMAXSA-N (2E,4E)-2,4-hexadien-1-ol Chemical compound C\C=C\C=C\CO MEIRRNXMZYDVDW-MQQKCMAXSA-N 0.000 description 1
- FDOPVENYMZRARC-UHFFFAOYSA-N 1,1,1,2,2-pentafluoropropane Chemical compound CC(F)(F)C(F)(F)F FDOPVENYMZRARC-UHFFFAOYSA-N 0.000 description 1
- LVGUZGTVOIAKKC-UHFFFAOYSA-N 1,1,1,2-tetrafluoroethane Chemical compound FCC(F)(F)F LVGUZGTVOIAKKC-UHFFFAOYSA-N 0.000 description 1
- PFFGXVGPSGJOBV-UHFFFAOYSA-N 1,1,1,3-tetrafluoropropane Chemical compound FCCC(F)(F)F PFFGXVGPSGJOBV-UHFFFAOYSA-N 0.000 description 1
- WXGNWUVNYMJENI-UHFFFAOYSA-N 1,1,2,2-tetrafluoroethane Chemical compound FC(F)C(F)F WXGNWUVNYMJENI-UHFFFAOYSA-N 0.000 description 1
- YACLCMMBHTUQON-UHFFFAOYSA-N 1-chloro-1-fluoroethane Chemical compound CC(F)Cl YACLCMMBHTUQON-UHFFFAOYSA-N 0.000 description 1
- VOPWNXZWBYDODV-UHFFFAOYSA-N Chlorodifluoromethane Chemical class FC(F)Cl VOPWNXZWBYDODV-UHFFFAOYSA-N 0.000 description 1
- KGWDUNBJIMUFAP-KVVVOXFISA-N Ethanolamine Oleate Chemical compound NCCO.CCCCCCCC\C=C/CCCCCCCC(O)=O KGWDUNBJIMUFAP-KVVVOXFISA-N 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229920001774 Perfluoroether Polymers 0.000 description 1
- 229930182556 Polyacetal Natural products 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 1
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 235000013844 butane Nutrition 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- KYKAJFCTULSVSH-UHFFFAOYSA-N chloro(fluoro)methane Chemical class F[C]Cl KYKAJFCTULSVSH-UHFFFAOYSA-N 0.000 description 1
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 150000001983 dialkylethers Chemical class 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000011094 fiberboard Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- UKACHOXRXFQJFN-UHFFFAOYSA-N heptafluoropropane Chemical compound FC(F)C(F)(F)C(F)(F)F UKACHOXRXFQJFN-UHFFFAOYSA-N 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Substances CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000012774 insulation material Substances 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000007562 laser obscuration time method Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- SYJXFKPQNSDJLI-HKEUSBCWSA-N neamine Chemical compound N[C@@H]1[C@@H](O)[C@H](O)[C@@H](CN)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@H](N)C[C@@H]1N SYJXFKPQNSDJLI-HKEUSBCWSA-N 0.000 description 1
- UJMWVICAENGCRF-UHFFFAOYSA-N oxygen difluoride Chemical class FOF UJMWVICAENGCRF-UHFFFAOYSA-N 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 229940059574 pentaerithrityl Drugs 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- MSSNHSVIGIHOJA-UHFFFAOYSA-N pentafluoropropane Chemical compound FC(F)CC(F)(F)F MSSNHSVIGIHOJA-UHFFFAOYSA-N 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920006149 polyester-amide block copolymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920006295 polythiol Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000011493 spray foam Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- 229940029284 trichlorofluoromethane Drugs 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/122—Hydrogen, oxygen, CO2, nitrogen or noble gases
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2110/00—Foam properties
- C08G2110/0025—Foam properties rigid
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2110/00—Foam properties
- C08G2110/0041—Foam properties having specified density
- C08G2110/005—< 50kg/m3
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2205/00—Foams characterised by their properties
- C08J2205/10—Rigid foams
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
Abstract
Process for preparing rigid polyurethane or urethane-modified polyisocyanurate foams comprising the step of reacting an organic polyisocyanate with a polyfunctional isocyanate-reactive component in the presence of a blowing agent mixture comprising from 50 to 90 % by weight of cyclopentane and from 10 to 50 % by weight of a mixture comprising isopentane and/or n-pentane and isobutane and/or n-butane wherein the weight ratio of isopentane and/or n-pentane over isobutane and/or n-butane is between 5/95 and 95/5.
Description
The present invention relates to the manufacture method of urethane or urethane-modified poly-isocyanurate rigid foam and the prepared porous plastics of method thus, the novel compositions that also relates to this method and adopted.
Urethane and the urethane-modified common manufacture method of poly-isocyanurate rigid foam are that the suitable polyisocyanates and the compound of isocyanate-reactive (normally polyvalent alcohol) are reacted.One of purposes of this type of foam is as thermal insulation material, for example is used as the structured material of refrigerating plant.The heat-insulating property of rigid foam depends on many factors, for the rigid foam of closed-cell, comprising the size of abscess and the thermal conductivity of abscess inclusion.
In producing urethane and urethane-modified polyisocyanurate foamed plastics extensively employing be the fluorochlorohydrocarbon of perhalogeno, especially trichlorofluoromethane (CFC-11) as a class material of whipping agent.These whipping agents, especially CFC-11 are because of having extremely low thermal conductivity so can make prepared rigid foam possess effective heat-insulating property.Recently people pay close attention to fluorochlorohydrocarbon to causing the potentiality of ozone-depleting in the atmosphere; this just causes pressing for the reaction system that exploitation can replacement fluorine chlorocarbon whipping agent; this class equivalent material is that environment protection institute is receptible, and has necessary performance by the porous plastics of its manufacturing in many Application Areass.
The substituting whipping agent of this type of that is proposed in prior art comprises that hydrochlorofluorocarsolvent, hydrofluorocarbon and particularly hydro carbons are alkane and cycloalkane, as Trimethylmethane, Skellysolve A, iso-pentane, pentamethylene with and composition thereof.
The mixture of pentamethylene and Trimethylmethane preferably.As described the sort of in European patent EP 421269; The mixture that also has pentamethylene and iso-pentane or Skellysolve A, the sort of described in WO94/25514.
The object of the present invention is to provide a kind of hydrocarbon blowing agent mixture, this mixture can improve the performance of porous plastics, can make processing become easy simultaneously again.
Why these purposes of the present invention can reach, be because in make urethane and urethane-modified poly-isocyanurate rigid foam by polyisocyanates and isocyanate-reactive component, used a kind of blowing agent blends, this mixture comprises pentamethylene and the iso-pentane of 10～50wt% and/or the mixture of Skellysolve A and Trimethylmethane and/or normal butane of 50～90wt%, and wherein the weight ratio of iso-pentane and/or Skellysolve A and Trimethylmethane and/or normal butane is 5/95～95/5.
Adopt this blowing agent blends can make processing become more easy, and can improve heat-insulating property than the mixture that adopts pentamethylene and Trimethylmethane.
Than adopting pentamethylene and exclusive OR Skellysolve A mixture, adopt mixture of the present invention can make the porous plastics that dimensional stability is improved, this is because can obtain more low-density stable foam body.
Best, the content of pentamethylene is 60～90wt%, is 60～80wt%, the most preferred 70～75wt% of being more preferably in said blowing agent blends; The weight ratio of iso-pentane and/or Skellysolve A and Trimethylmethane and/or normal butane is preferably 90/10～20/80, more preferably be 75/25～25/75, most preferred be 2/1～1/2.
In blowing agent blends of the present invention, adopt iso-pentane to be better than the employing Skellysolve A, same, adopt Trimethylmethane to be better than the employing normal butane.
The example of used preferred blowing agent blends can be listed below among the present invention: the mixture that contains 70wt% pentamethylene, 20wt% iso-pentane and 10wt% Trimethylmethane, the mixture that contains 70wt% pentamethylene, 10wt% iso-pentane and 20wt% Trimethylmethane contains the mixture of 75wt% pentamethylene, 15wt% iso-pentane and 10wt% Trimethylmethane.
The suitable isocyanate-reactive component that will adopt among the present invention comprises those known isocyanate-reactive components that are used to make urethane or urethane-modified poly-isocyanurate rigid foam in any this area.For preparation rigid foam particularly importantly polyalcohols and polyol blends, its average hydroxyl number is 300～1000, especially 300～700mg KOH/g, and its hydroxy functionality is 2～8, especially 3～8.Suitable polyvalent alcohol expounds adequately in prior art, comprising the oxirane hydro carbons, contains the product of the initiator for reaction of 2～8 reactive hydrogen atoms as oxyethane and/or propylene oxide and each molecule.Suitable initiator comprises: polyalcohols such as glycerine, TriMethylolPropane(TMP), trolamine, tetramethylolmethane, sorbyl alcohol and sucrose, polyamines class such as quadrol, tolylene diamine (TDA), diaminodiphenylmethane (DADPM) and polymethylene polyphenylene polyamines and alkamine such as thanomin and diethanolamine, and the mixture of this type of initiator.Other suitable polymeric polyalcohols comprises by the polyvalent alcohol of the ethylene glycol of suitable proportion and higher functionality and dicarboxylic acid or poly carboxylic acid condensation and the polyester that makes.Also have another kind of suitable polymerized polyalcohol, comprise hydroxy-end capped polythioether, polymeric amide, polyesteramide, polycarbonate, polyacetal, polyolefine and polysiloxane.The particularly preferred isocyanate-reactive compound that plan is used for the hydrocarbon foaming system is the polyvalent alcohol that the polyether glycol that amine causes, especially aromatic amine cause.The polyether glycol that causes as TDA-and DADPM, as in WO97/48748, narrated those, the content of this patent is incorporated this paper into as a reference.
The suitable organic multiple isocyanate that is used for the inventive method comprises that this area is in order to make any in urethane or urethane-modified known those polyisocyanates of poly-isocyanurate rigid foam, especially aromatic polyisocyanate as with its 2,4 ＇-, 2,2 ＇-and the '-diphenylmethane diisocyanate that provides of 4,4 ＇-isomer and composition thereof form; The mixture of '-diphenylmethane diisocyanate (MDI) and its oligopolymer, this oligopolymer is referred to as " thick " or polymeric MDI (polymethylene polyphenylene(poly)isocyanate) in the art, and the functionality of its isocyanic ester is greater than 2; With its 2,4-and 2, the tolylene diisocyanate that 6-isomer and composition thereof form provides; L,5 naphthylene diisocyanate; And 1, the 4-phenylene vulcabond.Other organic multiple isocyanate that can mention comprises aliphatic vulcabond, as isophorone diisocyanate, 1, and 6-hexane diisocyanate and 4,4 ＇-dicyclohexyl methane diisocyanate.
The consumption of polyisocyantates composition and many functional group isocyanates's reactive composition that will react with it depends on the character of the urethane that will make or urethane-modified poly-isocyanurate rigid foam, and this point is easy to make decision for a person skilled in the art.
Known other pneumatogen that is used to make rigid polyurethane foams also can use with hydrocarbon blowing agent mixture of the present invention.The example of these pneumatogens comprises other hydro carbons, dialkyl ether, ring alkylidene group ethers and ketone, fluoro ethers, chlorofluorocarbon class, perfluoroalkanes, and especially hydrochlorofluorocarsolvent class and hydrofluorocarbon class.
The example of suitable hydrochlorofluorocarsolvent class comprises 1-chloro-1,2-C2H4F2 C2H4F2,1-chloro-2,2-C2H4F2 C2H4F2,1-chloro-1,1-C2H4F2 C2H4F2,1,1-two chloro-1-fluoroethane and monochlorodifluoromethanes.
Suitable hydrofluorocarbon class comprises 1,1,1,2-Tetrafluoroethane, 1,1,2,2-Tetrafluoroethane, trifluoromethane, heptafluoro-propane, 1,1,1-Halothane, 1,1,2-Halothane, 1,1,1,2,2-pentafluoropropane, 1,1,1,3-tetrafluoropropane, 1,1,1,3,3-pentafluoropropane and 1,1,1,3,3-five fluorine normal butanes.
Usually the compound with water or other release of carbon dioxide uses with said these pneumatogens.When making water as chemical blowing promotor, it is 0.2～5wt% of benchmark that its consumption is generally in the isocyanate-reactive compound, is preferably 0.5～3wt%.
The whipping agent total amount that will use in the reaction system of making foamed polymer material is easy to make decision by those skilled in the art, is 2～25% of benchmark and be generally in the reaction system gross weight.
Except polyisocyanates and many functional group isocyanates's reactive composition and blowing agent blends, make and generally also to comprise one or more auxiliary agent or additives commonly used in making urethane or urethane-modified poly-isocyanurate rigid foam prescription in the reaction mixture of porous plastics.The optional additive of this class comprises the filler of the haloalkylphosphate of low molecular weight polyols, foaming stabilizer or the tensio-active agent of linking agent such as trolamine and so on such as the tin compound of siloxanes-oxyalkylene copolymers, urethane catalyst such as stannous octoate or dibutyl tin laurate and so on or tertiary amine, isocyanate catalyst, fire retardant such as tricresyl phosphate chloropropyl ester of dimethylcyclohexylam,ne or triethylenediamine and so on and so on and carbon black and so on.
Making according to the inventive method in the operation of rigid foam, the hybrid system of a known step foaming, prepolymer or half pre-thing technology and routine can be combined use, rigid foam then can be made sheet material, mo(u)lded item, cavity stopping composition, spray foam body, frothing foam body or comprise such as other materials such as fiber board, plasterboard, plastics, paper or metals at interior laminated plate material.
Way is easily in many Application Areass, is being that production of polyurethane provides various components with the form based on elementary polyisocyanates and isocyanate-reactive component pre-mixed ingredients separately.Specifically, many reaction systems all adopt a kind of polyisocyanates reactive composition as the main additive of whipping agent and so on that contains except polyisocyanates reactive component or its various ingredients.
Therefore, the present invention also provides a kind of polyisocyanates reactive composition that comprises blowing agent blends of the present invention.
The present invention is illustrated with following embodiment, but is not subjected to the restriction of these embodiment.
Embodiment 1～5
Fill inner container of icebox with the urethane batching that contains listed each component in the following table 1.
Polyvalent alcohol is the polyhydric alcohol composition of a kind of OH value for 390mg KOH/g; Isocyanic ester is poly-MDI composition.
Follow the tracks of reaction process with cream time (reaction mixture begins the required time of foaming) and wire drawing time (reaction mixture is reached the required time of transition point of crosslinked body by fluid).
According to the ISO845 standard test free initial density-emitting of porous plastics.
The measuring method of flow index is as follows: with reference foam doses of plastics mobile height setting in a special pipe of certainweight is 1.00; Again sample foams doses of plastics mobile height in this same pipe of identical weight is measured and compared with the height of this reference foam doses of plastics.The porous plastics (embodiment 1) of pentamethylene foaming is got and is made the reference foam plastics.
λ value under having measured 10 ℃ according to ASTM C518 method.
Measure the foaming degree of porous plastics with appearance method.
Filling weight represents to be filled with the inner container of icebox of porous plastics and the weight difference between the unfilled inner container of icebox, and to a heavy-walled and have the monomer accumulated ice case of model 1 of simple airflow circulation mode and the refrigerator of a combined model 2 with compound airflow circulation mode has been measured this filling weight.
Oppositely heat leak has determined when reaching stable state (power loss) rate the power loss (thermal conduction) by inner container of icebox.Its measuring method is as follows: the inner container of icebox connection power supply of being closed and regulation and control are good; Form hot-fluid from its inside and outside surface; After setting up a kind of steady state (thermal equilibrium), measure the power that is consumed; The RHL value is exactly for keeping the power (is unit with the watt) of the required consumption of inside and outside predetermined temperature difference (this moment, the used temperature difference was 20 ℃).In table 1, the RHL of sample foams plastics represents that with respect to reference foam plastics (embodiment 1) latter's RHL is set at 100.Only the refrigerator of model 1 has been measured its RHL value.
Measurement result is shown in the following table 1.
Table 1
| The embodiment sequence number | ????1 | ??2 | ????3 | ????4 | ????5 | |
| Polyvalent alcohol | Weight part | ????100 | ?100 | ????100 | ????100 | ????100 |
| Water | Weight part | ????2.1 | ?2.1 | ????2.1 | ????2.1 | ????2.1 |
| Pentamethylene | Weight part | ????15 | ?10.5 | ????10.5 | ????10.5 | ????10.5 |
| Iso-pentane | Weight part | ?4.5 | ????2.0 | ????1.0 | ||
| Trimethylmethane | Weight part | ????3.5 | ????1.5 | ????2.5 | ||
| Isocyanic ester | Weight part | ????144 | ?144 | ????144 | ????144 | ????144 |
| Emulsification times | Second | ????4 | ?4 | ????3 | ||
| The wire drawing time | Second | ????38 | ?37 | ????38 | ????37 | ????38 |
| Free initial density-emitting | kg/m 3 | ????23.2 | ?22.5 | ????22.7 | ????22.9 | ????22.7 |
| Flow index | ????1.00 | ?1.15 | ????1.06 | ????1.12 | ????1.08 | |
| ????λ | mW/mK | ????20.0 | ?20.3 | ????20.8 | ????20.3 | ????20.5 |
| Foaming degree | Do not have | Do not have | Severe | Do not have | Slightly | |
| Filling weight | ||||||
| Model 1 | g | ????3300 | ?3000 | ????2900 | ????3000 | ????3000 |
| Model 2 | g | ????6600 | ?6000 | ????6000 | ????5800 | ????5900 |
| Oppositely heat leak | ％?? | ????100 | ?101 | ????104 | ????101 | ????103 |
The result shows in the table, adopts the porous plastics (embodiment 4 and 5) according to blowing agent blends foaming of the present invention to have lower density than the porous plastics of only using pentamethylene (embodiment 1) foaming; In addition, the flowability of porous plastics batching of the present invention is improved, thereby causes lower refrigerator filling weight.Compare with the porous plastics that adopts pentamethylene/iso-pentane mixture (embodiment 2) foaming, porous plastics of the present invention also obtains lower filling weight.
Compare with the porous plastics (embodiment 3) that adopts pentamethylene/Trimethylmethane mixture foaming, porous plastics of the present invention batching also obtains good mobility (lower filling weight, especially more obvious for compound refrigerator) and heat-insulating property (λ and energy expenditure) preferably.
Claims (8)
1. make the method for urethane or urethane-modified poly-isocyanurate rigid foam, this method comprises the step that a kind of organic multiple isocyanate and a kind of many functional group isocyanates's reactive component are reacted in the presence of a kind of blowing agent blends, this blowing agent blends comprises pentamethylene and the iso-pentane of 10～50wt% and/or the mixture of Skellysolve A and Trimethylmethane and/or normal butane of 50～90wt%, and wherein iso-pentane and/or Skellysolve A are 5/95～95/5 to the weight ratio of Trimethylmethane and/or normal butane.
2. according to the process of claim 1 wherein that the content of pentamethylene is 60～80wt% in blowing agent blends, and the content of iso-pentane and/or Skellysolve A and Trimethylmethane and/or normal butane mixture is 20～40wt%.
3. according to the method for claim 1 or 2, wherein iso-pentane and/or Skellysolve A are 75/25～25/75 to the weight ratio of Trimethylmethane and/or normal butane.
4. according to the method for claim 3, wherein iso-pentane and/or Skellysolve A are 2/1～1/2 to the weight ratio of Trimethylmethane and/or normal butane.
5. according to any one method in the aforementioned claim, wherein said blowing agent blends comprises pentamethylene, iso-pentane and Trimethylmethane.
6. according to the method for claim 5, wherein said blowing agent blends is selected from following mixture: the mixture that is made of 70wt% pentamethylene, 20wt% iso-pentane, 10wt% Trimethylmethane, the mixture that constitutes by 70wt% pentamethylene, 10wt% iso-pentane, 20wt% Trimethylmethane, the mixture that constitutes by 75wt% pentamethylene, 15wt% iso-pentane, 10wt% Trimethylmethane.
7. urethane that makes according to the method for any one defined in the aforementioned claim or urethane-modified poly-isocyanurate rigid foam.
8. the isocyanate-reactive composition that comprises any one defined blowing agent blends in the claim 1～6.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP98103259 | 1998-02-25 | ||
| EP98103259.2 | 1998-02-25 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1292013A true CN1292013A (en) | 2001-04-18 |
Family
ID=8231475
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN99803273A Pending CN1292013A (en) | 1998-02-25 | 1999-01-21 | Process for rigid polyurethane foams |
Country Status (16)
| Country | Link |
|---|---|
| US (1) | US20010014703A1 (en) |
| EP (1) | EP1058709A1 (en) |
| JP (1) | JP2002504609A (en) |
| KR (1) | KR20010041256A (en) |
| CN (1) | CN1292013A (en) |
| AR (1) | AR018565A1 (en) |
| AU (1) | AU748858B2 (en) |
| BR (1) | BR9908189A (en) |
| CA (1) | CA2318300A1 (en) |
| HU (1) | HUP0105020A2 (en) |
| ID (1) | ID25632A (en) |
| NZ (1) | NZ505756A (en) |
| PL (1) | PL342545A1 (en) |
| SK (1) | SK12712000A3 (en) |
| TR (1) | TR200002470T2 (en) |
| WO (1) | WO1999043742A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101654507B (en) * | 2009-09-30 | 2011-09-28 | 大庆油田有限责任公司 | Low temperature high strength fluorine-free polyurethane foam heat insulation material |
| CN110343227A (en) * | 2019-08-09 | 2019-10-18 | 南京红宝丽聚氨酯有限公司 | A kind of hard polyurethane foams of extremely-low density and preparation method thereof |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6348515B1 (en) * | 2000-09-06 | 2002-02-19 | Atofina Chemicals, Inc. | Blowing agent blends |
| GB2553072B (en) * | 2015-05-22 | 2021-07-07 | Linde Ag | Blowing agent |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3933335C2 (en) * | 1989-10-06 | 1998-08-06 | Basf Ag | Process for the production of rigid polyurethane foams with low thermal conductivity and their use |
| DE4303659C2 (en) * | 1993-02-09 | 1996-09-05 | Bayer Ag | Use of mixtures of hydrocarbons and caprolactam hydrate as blowing agents in the production of foams based on isocyanate |
| GB9403334D0 (en) * | 1993-04-23 | 1994-04-13 | Ici Plc | Process for rigid polyurethane foams |
| US5519065A (en) * | 1994-03-11 | 1996-05-21 | Imperial Chemical Industries Plc | Process for rigid polyurethane foams |
| US5451615A (en) * | 1994-10-20 | 1995-09-19 | The Dow Chemical Company | Process for preparing polyurethane foam in the presence of a hydrocarbon blowing agent |
-
1999
- 1999-01-21 HU HU0105020A patent/HUP0105020A2/en unknown
- 1999-01-21 NZ NZ505756A patent/NZ505756A/en unknown
- 1999-01-21 ID IDW20001524A patent/ID25632A/en unknown
- 1999-01-21 SK SK1271-2000A patent/SK12712000A3/en unknown
- 1999-01-21 KR KR1020007009349A patent/KR20010041256A/en not_active Application Discontinuation
- 1999-01-21 CN CN99803273A patent/CN1292013A/en active Pending
- 1999-01-21 JP JP2000533488A patent/JP2002504609A/en not_active Withdrawn
- 1999-01-21 AU AU26206/99A patent/AU748858B2/en not_active Ceased
- 1999-01-21 CA CA002318300A patent/CA2318300A1/en not_active Abandoned
- 1999-01-21 TR TR2000/02470T patent/TR200002470T2/en unknown
- 1999-01-21 EP EP99906181A patent/EP1058709A1/en not_active Withdrawn
- 1999-01-21 BR BR9908189-0A patent/BR9908189A/en not_active Application Discontinuation
- 1999-01-21 PL PL99342545A patent/PL342545A1/en unknown
- 1999-01-21 WO PCT/EP1999/000382 patent/WO1999043742A1/en not_active Application Discontinuation
- 1999-02-22 US US09/253,956 patent/US20010014703A1/en not_active Abandoned
- 1999-02-24 AR ARP990100765A patent/AR018565A1/en unknown
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101654507B (en) * | 2009-09-30 | 2011-09-28 | 大庆油田有限责任公司 | Low temperature high strength fluorine-free polyurethane foam heat insulation material |
| CN110343227A (en) * | 2019-08-09 | 2019-10-18 | 南京红宝丽聚氨酯有限公司 | A kind of hard polyurethane foams of extremely-low density and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CA2318300A1 (en) | 1999-09-02 |
| BR9908189A (en) | 2000-10-24 |
| ID25632A (en) | 2000-10-19 |
| WO1999043742A1 (en) | 1999-09-02 |
| TR200002470T2 (en) | 2001-01-22 |
| JP2002504609A (en) | 2002-02-12 |
| HUP0105020A2 (en) | 2002-04-29 |
| EP1058709A1 (en) | 2000-12-13 |
| NZ505756A (en) | 2002-02-01 |
| SK12712000A3 (en) | 2001-02-12 |
| AU748858B2 (en) | 2002-06-13 |
| US20010014703A1 (en) | 2001-08-16 |
| KR20010041256A (en) | 2001-05-15 |
| PL342545A1 (en) | 2001-06-18 |
| AU2620699A (en) | 1999-09-15 |
| AR018565A1 (en) | 2001-11-28 |
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